US5624476A - Method and device for purifying gaseous effluents - Google Patents

Method and device for purifying gaseous effluents Download PDF

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Publication number
US5624476A
US5624476A US08/196,256 US19625694A US5624476A US 5624476 A US5624476 A US 5624476A US 19625694 A US19625694 A US 19625694A US 5624476 A US5624476 A US 5624476A
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liquid
stages
gas
accumulation tank
accumulation
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US08/196,256
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English (en)
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Charles Eyraud
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Ecoprocess SARL
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Ecoprocess SARL
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C3/00—Separating dispersed particles from gases or vapour, e.g. air, by electrostatic effect
    • B03C3/32—Transportable units, e.g. for cleaning room air
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C3/00—Separating dispersed particles from gases or vapour, e.g. air, by electrostatic effect
    • B03C3/01—Pretreatment of the gases prior to electrostatic precipitation
    • B03C3/014—Addition of water; Heat exchange, e.g. by condensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C3/00—Separating dispersed particles from gases or vapour, e.g. air, by electrostatic effect
    • B03C3/02—Plant or installations having external electricity supply
    • B03C3/16—Plant or installations having external electricity supply wet type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C3/00—Separating dispersed particles from gases or vapour, e.g. air, by electrostatic effect
    • B03C3/34—Constructional details or accessories or operation thereof
    • B03C3/88—Cleaning-out collected particles

Definitions

  • a gas can be purified highly efficiently by dispersing a liquid reactant between the electrodes of an electrostatic filter.
  • Several methods have been employed, proposed or patented in order to produce a liquid mist in this type of contactor between three media, respectively gaseous, liquid and solid:
  • An electrostatic reactor according to the invention has two functional features:
  • the structural and operational elements of an electrostatic reactor according to the invention are: the gas treatment line, the spray field, the module, the funnel field, the accumulation tank, the extraction tank, the concentration field, the dwell time, the transfer liquid, the electric field, the liquid treatment line.
  • the "gas treatment line” or “effects line” is formed by the succession of spray fields, at each of which the transfers and the reactions between the gas and the liquid mist occur, from the input to the output of the apparatus.
  • a “spray field” is the space occupied by a group of electrodes frontally irrigated using a curtain of highly dispersed liquid by pipes of atomizers distributed in a plane perpendicular to the gas flow. It corresponds to an "effect" of the gas/liquid transfer.
  • additional spraying is carried out at the upper part of a group of planar electrodes by means of the same liquid as that of the frontal spraying.
  • An additional spraying is also possible at the top of a group of tubular collector electrodes, the frontal spraying being carried out in this case at the base, that is to say at the gas input.
  • the composition of the spraying liquid may be the same for all the spray fields flowing into the same accumulation tank.
  • the first case allows the possibility of optimizing the treatment of the gas by a particular reactant at a single spray field
  • the second case is a contribution to the flow-back by a path other than that of the direct liquid transport from one accumulation tank to the next
  • the third case has the advantage of decreasing the entrainment by the gases, from one spray field to another, of the pollutants contained in excessively concentrated liquid vesicles.
  • the multiplication of the spray fields has two advantages
  • the flow rate, the composition and the spatial distribution of the primary mist can be adapted, at each spray field, to the local and temporal characteristics of the gas stream (temperature, humidity, chemical composition of the gases, continuous or discontinuous emission regime);
  • the “module” is a section of the gas treatment line. It itself has all the features of an electrostatic filter/washer, namely a casing containing the electrodes, the fluid inputs and outputs and the electrical supplies.
  • An electrostatic reactor according to the invention may consist of a single module, in this case of planar electrodes, it necessarily has several in the case of cylindrical electrodes, but it necessarily includes, in all cases, at least one concentration field having backflow and multiple stages.
  • a module may include one or more concentration fields with back-flow.
  • a concentration field with back-flow is necessarily formed by several modules, each constituting one spray field.
  • the apparatus which satisfies the specifications of the schedule of conditions may advantageously be produced by a suitable combination of standard modules, arranged in series and/or in parallel.
  • each module may be chosen as a function of the more or less corrosive local compositions of the gas and of the liquid along the treatment line for the two fluids.
  • the modular design overcomes to some extent the hindering of the gases at the top and at the bottom of the casing.
  • a "field of funnels" is the apparatus section to which an accumulation tank is assigned which collects, using one or more funnels, the sludge or the concentrated solutions which flow at the base of a spray field or several spray fields.
  • the liquid collected is partly recycled by spraying in the same field of funnels, allowing possible adaptations of its chemical composition, partly drawn off to produce the liquid flow-back from stage to stage, and partly withdrawn at the extraction tanks with a view to eliminating the undesirable transfer products by means of suitable separation methods (precipitation, sedimentation, filtration, centrifuging, pH adjustment, chemical reactions, etc.).
  • the “concentration field”, which ends in an extraction tank, is the apparatus section to which the concentration of certain transfer pollutants by liquid/gas contact with back-flow and multiple stages is devoted.
  • it therefore comprises several fields of funnels, that is to say several accumulation tanks constituting the stages.
  • cylindrical collector electrodes it necessarily comprises several modules and as many accumulation tank.
  • the electrostatic reactor according to the invention necessarily has at least one concentration field.
  • a “sequential dwell time” is the average time which the gas takes to cover a particular section of the treatment line: spray field, field of funnels, concentration field or gas treatment line.
  • spray field In the case of dust removal, it varies proportionately to the "surface area per unit volume of electrodes in the corresponding section", that is to say the surface area of electrodes contained in this section per standard cubic meter of gas passing through the apparatus in one hour.
  • modular production it can be varied by assigning a greater or lesser number of modules in series or in parallel to a particular treatment sequence.
  • a washer for the gas may be placed at the head or at the tail of the electrical purifier.
  • the number of degrees of freedom necessary for adjusting the characteristics of the purifier as a function of the rates of the chemical reactions in question and of the antipollution standards in force are thus available.
  • composition of the "transfer liquid” either in the nebulized state or in the state of run-off collected in the accumulation tanks, varies along the gas treatment line because, on the one hand, of the specificity of the reaction in question and, on the other hand, of the concentration with multiple stages and gas/liquid counterflow produced either by direct transport of the liquid from one accumulation tank to the next or by continuous or discontinuous partial spraying of a group of electrodes using the liquid coming from the accumulation tank of the adjacent stage or coming from a withdrawal and purification operation carried out at an extraction tank; during the spraying sequence, the end of the group of electrodes is correctly washed, but a part of the liquid mist and the pollutants which it contains are entrained from one stage to the next by convection, which effect is unfavourable for strong concentration of the sludge and for strong purification of the gas; during the stop sequence of the spraying, the drops are electrostatically precipitated at the stage where they are produced and therefore do not participate in the reentrainment of purities carried by the liquid mist.
  • the composition may also vary from one spray field to another if reactants are introduced directly into the irrigation pipes as a complement to those introduced into the tanks.
  • the composition of the "spraying liquid" is determined by the nature and the kinetic characters of the transfer reactions which are assigned to one spray field, one funnel field, or one concentration field. It most generally involves water containing soluble reactants, reactive or inert solids in the dispersed state, catalysts, optionally ionic or nonionic surfactant products or alternatively emulsified oil-absorbing substances.
  • An "electric field”, according to its classical definition, is the space occupied by one or more groups of electrodes supplied by one and the same electric generator.
  • the multiplication of the electric fields has well known advantages;
  • a “lane” is the space contained between the two collector electrodes on either side of an emitting electrode in the case of an electrostatic filter with planar geometry.
  • the "liquid treatment line” is that of the physical and chemical operations carried out on the concentrated liquids withdrawn at the extraction tanks with a view, on the one hand, to removing the undesirable products and, on the other hand, to partially or completely recycling, at suitably chosen points on the gas treatment line, the washing liquids thus totally or partially purified, and optionally regenerated reactants.
  • FIG. 1 is a view in longitudinal vertical section of a wet electrostatic filter with liquid/gas counterflow.
  • FIG. 2 is a plan view of the electrostatic filter represented by the preceding figure.
  • FIG. 3 is a view in vertical section of a bundle of tublar electrodes constituting one of the stages of a wet electrostatic filter with liquid/gas counterflow.
  • FIG. 4 is a plan view of the stage represented by the preceding figure.
  • FIG. 5 is a view in vertical section of a cylindrical collector electrode and of the corresponding emitting back-electrode, with various spray devices.
  • FIG. 6 is a view in vertical section of a spray field with vertical spray pipes and horizontal spray pipes, the run-off from the electrodes being collected by two funnels into a single accumulation tank constituting one of the concentration stages of a planar wet electrostatic filter with liquid/gas counterflow.
  • FIG. 1 and FIG. 2 represent, diagrammatically and respectively in vertical and horizontal section, an apparatus with planar geometry having three "electric fields” 46, 47, and 48. It comprises a casing 44, four spray fields 5, 6, 7, 8, and three funnel fields 9, 10, 11, the first two 9 and 10 each including a single spray field, and the third 11 having two spray fields, 7 and 8.
  • Each of the spray fields includes three "lanes” such as 12 and are each irrigated by vertical spray pipes such as 13.
  • Planar collector electrodes 3 define the lanes 12, and the dashed lines designate emitter electrodes 1 centered in each lane 12.
  • Other pipes such as 19 ensure the water vapour saturation of the gas entering into the apparatus.
  • These spray pipes 19 may advantageously form part of a head stage assigned to drying the sludge by the sensible heat of the gas in order finally to obtain solid or pasty products.
  • Two accumulation tanks 17 and 18 participate in a concentration field having two stages whose back-flow passes through the pipe 30, the tank 17 being an extraction tank as is the tank 16.
  • Ceramic or silica components 33 support the emitting electrodes and insulate them from the earth 45.
  • the reactants are introduced into the accumulation tanks at 23, and optionally, and for some of them, directly into the spraying pipes at 24.
  • the undesirable products are removed in the liquid treatment line including separation units 25 and 26 operating on withdrawals from the extraction tanks 16 and 17.
  • the tanks 16, 17 and 18 may optionally participate in the back-flow concentration of certain pollutants not removed at 26 if the incompletely purified liquid is transported by the pipeline 27 to the accumulation tank 16.
  • the three funnel fields constitute a back-flow concentration field for these particular pollutants.
  • the undesirable products are extracted from the liquid treatment line at 31, and 32, in the form of optionally upgradable solid precipitates, highly concentrated sludge intended for discharge, industrially recyclable solutions, or completely or partially purified liquid recycled into the gas treatment line through pipelines such as 22, 28, 27 or 29.
  • FIG. 3 and FIG. 4 represent, diagrammatically and respectively in vertical and horizontal section, at the same time a module and spray field 6.
  • a frontal spraying pipe 13 is provided in the spray field 6.
  • the three accumulation tanks 16, 17 and 18 participate in a back-flow concentration field consisting of three modules such as 6.
  • Cylindrical electrodes such as 4 are fastened to a plate 34.
  • the emitting electrodes such as 2, which carry asperities such as 35 having electric field effect, are suspended from a network of beams 36 supported and insulated from the earth by ceramic or vitreous fused silica blocks such as 33.
  • An intake 37 provides air that sweeps through the protective case 38 of the insulator 33 which is, furthermore, optionally heated and thus protected from moisture and contact with the gas to be treated.
  • An intake 20 and an outlet 21 for the gas are also provided along with a high-voltage terminal 39.
  • FIG. 5, which relates to the case of a cylindrical collector electrode 4, represents the frontal spraying pipe 13 arranged at the base of the cylinder at the gas intake, and the additional spraying device making it possible to supply the top of the emitting electrode 2 with run-off water.
  • This liquid is provided either by primary spraying carried out using atomizers such as 14 and is then collected partly by a conical collar 40 which flares upwards and is perforated at its connection with the electrode 2, or by electrostatic nebulizing of the liquid 41 coming from the same primary spraying and collected by run-off in the conical collar 42 which is flared upwards and fastened by its base to the top of the collector electrode.
  • FIG. 6, which relates to planar electrodes, represents the single spray field of a field of funnels 10 (itself belonging to a concentration field with back-flow having at least three stages 16, 17, 18), the atomization pipes of which are of three types: vertical pipes 13 arranged frontally in front of a group of planar electrodes 6, horizontal pipes 14 that irrigate the first part of the group of electrodes 6 from above and are supplied by the same recycled liquid from the accumulation tank 17. Horizontal pipes 15 irrigate, continuously or discontinuously, the second part of the group of electrodes 6, also from above, but are supplied with the liquid coming from the accumulation tank 18.
  • This third type of pipe where it exists, constitutes one of the liquid back-flow paths from the stage 11 to the stage 9, the other back-flow path being that of the pipeline 30 which directly conveys, by gravity or by means of a pump, the liquid from the tank 18 to the tank 16.
  • the direction of the gas flow is designated as 43.
  • the reactor includes a field of funnels or a final module intended for cumulative analysis of the traces of harmful products, the continuous metering of which becomes impossible in the case of excessively severe standards.
  • the reactor constitutes a mobile unit for cumulative analysis of industrial gaseous effluents.

Landscapes

  • Treating Waste Gases (AREA)
  • Electrostatic Separation (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Gas Separation By Absorption (AREA)
US08/196,256 1991-08-21 1992-08-20 Method and device for purifying gaseous effluents Expired - Fee Related US5624476A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9110616A FR2680474B1 (fr) 1991-08-21 1991-08-21 Reacteur electrostatique a contacts gaz liquide solide a contre courant gaz liquide et a etages multiples pour l'epuration d'un gaz et des liquides de transfert.
FR9110616 1991-08-21
PCT/FR1992/000811 WO1993003849A1 (fr) 1991-08-21 1992-08-20 Precipitateur electrostatique humide

Publications (1)

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US5624476A true US5624476A (en) 1997-04-29

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US08/196,256 Expired - Fee Related US5624476A (en) 1991-08-21 1992-08-20 Method and device for purifying gaseous effluents

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US (1) US5624476A (ja)
EP (1) EP0600011B1 (ja)
JP (1) JPH06509976A (ja)
AT (1) ATE145157T1 (ja)
CA (1) CA2115987C (ja)
DE (1) DE69215229T2 (ja)
ES (1) ES2094368T3 (ja)
FR (1) FR2680474B1 (ja)
OA (1) OA09886A (ja)
WO (1) WO1993003849A1 (ja)

Cited By (33)

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US5827352A (en) * 1997-04-16 1998-10-27 Electric Power Research Institute, Inc. Method for removing mercury from a gas stream and apparatus for same
US6156098A (en) * 1999-02-10 2000-12-05 Richards; Clyde N. Charged droplet gas scrubber apparatus and method
EP1075872A2 (en) * 1999-08-13 2001-02-14 Mitsubishi Heavy Industries, Ltd. Electrostatic dust collector and electrostatic method for collecting dust
US6302945B1 (en) * 1999-06-11 2001-10-16 Electric Power Research Institute, Incorporated Electrostatic precipitator for removing SO2
US6488740B1 (en) * 2000-03-01 2002-12-03 Electric Power Research Institute, Inc. Apparatus and method for decreasing contaminants present in a flue gas stream
US20040202701A1 (en) * 1999-12-27 2004-10-14 Kimberly-Clark Worldwide, Inc. Modified siloxane yielding transferring benefits from soft tissue products
US20060093975A1 (en) * 2004-10-29 2006-05-04 Eisenmann Corporation Natural gas injection system for regenerative thermal oxidizer
US20060185511A1 (en) * 2005-02-24 2006-08-24 Tepper Gary C Contaminant extraction systems, methods and apparatuses
US20060226373A1 (en) * 2005-03-02 2006-10-12 Eisenmann Corporation Wet electrostatic precipitator for treating oxidized biomass effluent
US20060230938A1 (en) * 2005-04-15 2006-10-19 Eisenmann Corporation Method and apparatus for flue gas desulphurization
US20060261265A1 (en) * 2005-03-02 2006-11-23 Eisenmann Corporation Dual flow wet electrostatic precipitator
US20070009411A1 (en) * 2005-07-08 2007-01-11 Eisenmann Corporation Method and apparatus for particulate removal and undesirable vapor scrubbing from a moving gas stream
WO2007056566A1 (en) * 2005-11-09 2007-05-18 Sarnoff Corporation Air purification system and method
US20070128090A1 (en) * 2005-12-06 2007-06-07 Eisenmann Corporation Wet electrostatic liquid film oxidizing reactor apparatus and method for removal of NOx, SOx, mercury, acid droplets, heavy metals and ash particles from a moving gas
US20070205307A1 (en) * 2006-03-03 2007-09-06 Kozyuk Oleg V Device and method for creating hydrodynamic cavitation in fluids
US20080121106A1 (en) * 2006-05-18 2008-05-29 Tepper Gary C Contaminant extraction systems, methods, and apparatuses
US20080216658A1 (en) * 2007-03-05 2008-09-11 Hitachi Plant Technologies, Ltd. Wet-type electrostatic precipitator
US20090114092A1 (en) * 2006-06-07 2009-05-07 Sune Bengtsson Wet electrostatic precipitator
EP2072108A1 (en) * 2007-12-18 2009-06-24 B & B INGG. S.p.A. Filter apparatus and method of filtering aeriform substances
US20090241579A1 (en) * 2006-06-15 2009-10-01 Kanji Motegi Liquid treatment apparatus, air conditioning system, and humidifier
US20090241781A1 (en) * 2008-03-27 2009-10-01 Triscori Ronald J Hybrid wet electrostatic precipitator
US20090263293A1 (en) * 2006-05-19 2009-10-22 Kanji Motegi Electric discharge device and air purification device
US7662348B2 (en) 1998-11-05 2010-02-16 Sharper Image Acquistion LLC Air conditioner devices
US7695690B2 (en) 1998-11-05 2010-04-13 Tessera, Inc. Air treatment apparatus having multiple downstream electrodes
US7724492B2 (en) 2003-09-05 2010-05-25 Tessera, Inc. Emitter electrode having a strip shape
US7767169B2 (en) 2003-12-11 2010-08-03 Sharper Image Acquisition Llc Electro-kinetic air transporter-conditioner system and method to oxidize volatile organic compounds
US7833322B2 (en) 2006-02-28 2010-11-16 Sharper Image Acquisition Llc Air treatment apparatus having a voltage control device responsive to current sensing
US7897118B2 (en) 2004-07-23 2011-03-01 Sharper Image Acquisition Llc Air conditioner device with removable driver electrodes
US7906080B1 (en) 2003-09-05 2011-03-15 Sharper Image Acquisition Llc Air treatment apparatus having a liquid holder and a bipolar ionization device
US7959869B2 (en) 1998-11-05 2011-06-14 Sharper Image Acquisition Llc Air treatment apparatus with a circuit operable to sense arcing
US8043573B2 (en) 2004-02-18 2011-10-25 Tessera, Inc. Electro-kinetic air transporter with mechanism for emitter electrode travel past cleaning member
CN104069720A (zh) * 2014-07-12 2014-10-01 苏州克利亚环保科技有限公司 工业有机废气废水综合处理装置
CN108273662A (zh) * 2018-01-05 2018-07-13 老肯医疗科技股份有限公司 一种用于城市除雾霾的空气净化器

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KR101885240B1 (ko) * 2017-10-20 2018-08-03 주식회사 애니텍 배기가스에 포함된 입자상 물질 제거를 위한 정전 분무 방식의 전기 집진 시스템
CN111482146B (zh) * 2020-04-17 2022-02-22 中国石油化工股份有限公司 三相分离器、三相反应器以及三相反应方法

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Cited By (52)

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Publication number Priority date Publication date Assignee Title
US5827352A (en) * 1997-04-16 1998-10-27 Electric Power Research Institute, Inc. Method for removing mercury from a gas stream and apparatus for same
US7695690B2 (en) 1998-11-05 2010-04-13 Tessera, Inc. Air treatment apparatus having multiple downstream electrodes
USRE41812E1 (en) 1998-11-05 2010-10-12 Sharper Image Acquisition Llc Electro-kinetic air transporter-conditioner
US7959869B2 (en) 1998-11-05 2011-06-14 Sharper Image Acquisition Llc Air treatment apparatus with a circuit operable to sense arcing
US7976615B2 (en) 1998-11-05 2011-07-12 Tessera, Inc. Electro-kinetic air mover with upstream focus electrode surfaces
US7662348B2 (en) 1998-11-05 2010-02-16 Sharper Image Acquistion LLC Air conditioner devices
US8425658B2 (en) 1998-11-05 2013-04-23 Tessera, Inc. Electrode cleaning in an electro-kinetic air mover
US6156098A (en) * 1999-02-10 2000-12-05 Richards; Clyde N. Charged droplet gas scrubber apparatus and method
US6302945B1 (en) * 1999-06-11 2001-10-16 Electric Power Research Institute, Incorporated Electrostatic precipitator for removing SO2
US6602329B2 (en) * 1999-08-13 2003-08-05 Mitsubishi Heavy Industries, Ltd. Dust collector
US6500240B1 (en) 1999-08-13 2002-12-31 Mitsubishi Heavy Industries, Ltd. Dust collector
EP1075872A2 (en) * 1999-08-13 2001-02-14 Mitsubishi Heavy Industries, Ltd. Electrostatic dust collector and electrostatic method for collecting dust
EP1075872A3 (en) * 1999-08-13 2001-03-28 Mitsubishi Heavy Industries, Ltd. Electrostatic dust collector and electrostatic method for collecting dust
US20040202701A1 (en) * 1999-12-27 2004-10-14 Kimberly-Clark Worldwide, Inc. Modified siloxane yielding transferring benefits from soft tissue products
US6488740B1 (en) * 2000-03-01 2002-12-03 Electric Power Research Institute, Inc. Apparatus and method for decreasing contaminants present in a flue gas stream
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OA09886A (fr) 1994-09-15
JPH06509976A (ja) 1994-11-10
ATE145157T1 (de) 1996-11-15
FR2680474B1 (fr) 1995-09-08
FR2680474A1 (fr) 1993-02-26
CA2115987C (fr) 1998-11-03
EP0600011B1 (fr) 1996-11-13
DE69215229D1 (de) 1996-12-19
EP0600011A1 (fr) 1994-06-08
CA2115987A1 (fr) 1993-03-04
DE69215229T2 (de) 1997-03-06
ES2094368T3 (es) 1997-01-16
WO1993003849A1 (fr) 1993-03-04

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